Triplet 1,3-Diphenylpropynylidene (Ph−C−C−C−Ph)

• Published in: Journal of the American Chemical Society 2007-02, Vol.129 (8), p.2308-2315
• Main Authors: DePinto, Jeffrey T, deProphetis, Wendy A, Menke, Jessica L, McMahon, Robert J
• Format: Article
• Language: English
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja066300j

Photolysis (λ > 571 nm) of 1,3-diphenyldiazopropyne (9) affords triplet 1,3-diphenylpropynylidene (3), as characterized by IR, UV/vis, and EPR spectroscopy in low-temperature matrices. Two conformational isomers of triplet 3 are spectroscopically distinguishable. The initially formed, non-relaxed conformer is believed to reflect the geometry of the diazo precursor, as enforced by the rigid matrix. Annealing the matrix permits the structure to relax to the equilibrium D 2 d geometry. The highly symmetric equilibrium structure of 3 is best envisioned as a 1,3-allenic diradical. Density functional theory calculations suggest that the equilibrium structure does not exhibit a bond-localized structure that would be characteristic of an acetylenic carbene. Chemical trapping with O2, however, affords products that are familiar as carbene trapping products:  carbonyl oxide 10, ketone 11, and dioxirane 12. Irradiation (λ > 261 nm) of triplet 1,3-diphenylpropynylidene (3) results in cyclization to singlet diphenylcyclopropenylidene (6), a process that is photochemically reversible at λ = 232 nm. Diphenyl-1,2-propadienylidene (7) was not observed under any irradiation conditions.